Regeneration of PFAS-laden granular activated carbon by modified supercritical CO₂ extraction

Granular activated carbon (GAC) is widely used to treat contaminated per- and polyfluoroalkyl substances (PFAS) waste streams, resulting in the accumulation of large quantities of spent GAC that need to be landfilled or regenerated. A novel modified supercritical CO₂ (scCO₂) extraction for regeneration of spent GAC is developed. With the addition of organic solvents and acid modifiers, the procedure yielded >99% perfluorooctanoic acid (PFOA) desorption after a 60-min treatment in a continuous flow reactor. The mild extraction conditions at T ∼100 °C do not trigger the formation of volatile organic fluorine or changes in GAC sorbent properties. Mechanistically, the high miscibility of co-solvent/scCO₂ eliminates diffusion transport limitations, enabling rapid reagent and PFAS transport in a single-phase (gas-like) medium. The introduction of organic co-solvent and the absence of water reverses hydrophobic interactions between GAC and the PFAS. The acid modifier minimizes the electrostatic PFOA/GAC interactions by protonating the perfluorooctanoate ion and providing competition for active GAC sites. The approach offers an economically effective regeneration scheme, enabling the reuse of sorbents and yielding effluent with a high loading of PFAS that is amenable to subsequent end-of-life treatment technologies.